EP0497171B1 - Polycarbosilanes contenant hétéroatomes - Google Patents
Polycarbosilanes contenant hétéroatomes Download PDFInfo
- Publication number
- EP0497171B1 EP0497171B1 EP92100811A EP92100811A EP0497171B1 EP 0497171 B1 EP0497171 B1 EP 0497171B1 EP 92100811 A EP92100811 A EP 92100811A EP 92100811 A EP92100811 A EP 92100811A EP 0497171 B1 EP0497171 B1 EP 0497171B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- stands
- general formula
- polycarbosilanes
- heterocouple
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920003257 polycarbosilane Polymers 0.000 title claims abstract description 124
- 125000005842 heteroatom Chemical group 0.000 title claims abstract description 47
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 15
- 229910052796 boron Inorganic materials 0.000 claims abstract description 14
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 13
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 68
- -1 alkylene radical Chemical class 0.000 claims description 64
- 150000001875 compounds Chemical class 0.000 claims description 52
- 125000000217 alkyl group Chemical group 0.000 claims description 29
- 150000003254 radicals Chemical class 0.000 claims description 27
- 229910052783 alkali metal Inorganic materials 0.000 claims description 23
- 150000001340 alkali metals Chemical class 0.000 claims description 22
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 19
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 19
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 17
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 17
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 16
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 16
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 15
- 239000011777 magnesium Substances 0.000 claims description 14
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 13
- 229910052794 bromium Inorganic materials 0.000 claims description 13
- 239000000460 chlorine Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 229910052749 magnesium Inorganic materials 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 13
- 229910052801 chlorine Inorganic materials 0.000 claims description 12
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 11
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 150000002367 halogens Chemical class 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 229910052804 chromium Inorganic materials 0.000 claims description 8
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052718 tin Inorganic materials 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 5
- 229910052733 gallium Inorganic materials 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- 229910052785 arsenic Inorganic materials 0.000 claims description 4
- 150000005840 aryl radicals Chemical class 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 229910052711 selenium Inorganic materials 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- 229910052714 tellurium Inorganic materials 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 229910052745 lead Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 claims description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims 3
- 125000000392 cycloalkenyl group Chemical group 0.000 claims 2
- 239000010936 titanium Substances 0.000 abstract description 13
- 229910052710 silicon Inorganic materials 0.000 abstract description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract description 5
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 abstract description 5
- 229930195733 hydrocarbon Natural products 0.000 abstract description 5
- 239000010703 silicon Substances 0.000 abstract description 3
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 34
- 239000002904 solvent Substances 0.000 description 27
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 13
- 125000003118 aryl group Chemical group 0.000 description 12
- 239000000919 ceramic Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 10
- 239000008096 xylene Substances 0.000 description 10
- 239000000835 fiber Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- 239000000376 reactant Substances 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000011651 chromium Substances 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 6
- 238000002329 infrared spectrum Methods 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical class C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000010955 niobium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- 238000003747 Grignard reaction Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical group C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N anhydrous diethylene glycol Natural products OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- WIBYPHGWXYLWQX-UHFFFAOYSA-N methyl 2-bromo-2-chloroacetate Chemical compound COC(=O)C(Cl)Br WIBYPHGWXYLWQX-UHFFFAOYSA-N 0.000 description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 4
- 229910010271 silicon carbide Inorganic materials 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000001897 boron-11 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000011669 selenium Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 3
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 229910008045 Si-Si Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910006411 Si—Si Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 2
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 description 2
- 150000001649 bromium compounds Chemical class 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- XOYLJNJLGBYDTH-UHFFFAOYSA-M chlorogallium Chemical compound [Ga]Cl XOYLJNJLGBYDTH-UHFFFAOYSA-M 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- MKNXBRLZBFVUPV-UHFFFAOYSA-L cyclopenta-1,3-diene;dichlorotitanium Chemical compound Cl[Ti]Cl.C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 MKNXBRLZBFVUPV-UHFFFAOYSA-L 0.000 description 2
- PESYEWKSBIWTAK-UHFFFAOYSA-N cyclopenta-1,3-diene;titanium(2+) Chemical compound [Ti+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 PESYEWKSBIWTAK-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- BYLOHCRAPOSXLY-UHFFFAOYSA-N dichloro(diethyl)silane Chemical compound CC[Si](Cl)(Cl)CC BYLOHCRAPOSXLY-UHFFFAOYSA-N 0.000 description 2
- XNNRZLAWHHLCGP-UHFFFAOYSA-N dichloro(ethyl)borane Chemical compound CCB(Cl)Cl XNNRZLAWHHLCGP-UHFFFAOYSA-N 0.000 description 2
- NCQDQONETMHUMY-UHFFFAOYSA-N dichloro(phenyl)borane Chemical compound ClB(Cl)C1=CC=CC=C1 NCQDQONETMHUMY-UHFFFAOYSA-N 0.000 description 2
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- BLJHFCVPKWOHJX-UHFFFAOYSA-N ethylgallium Chemical group CC[Ga] BLJHFCVPKWOHJX-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 238000007380 fibre production Methods 0.000 description 2
- 150000004795 grignard reagents Chemical class 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 150000004694 iodide salts Chemical class 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- MQBKFPBIERIQRQ-UHFFFAOYSA-N magnesium;cyclopenta-1,3-diene;cyclopentane Chemical compound [Mg+2].C=1C=C[CH-]C=1.[CH-]1[CH-][CH-][CH-][CH-]1 MQBKFPBIERIQRQ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- JOTBHEPHROWQDJ-UHFFFAOYSA-N methylgallium Chemical compound [Ga]C JOTBHEPHROWQDJ-UHFFFAOYSA-N 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- XPPWLXNXHSNMKC-UHFFFAOYSA-N phenylboron Chemical compound [B]C1=CC=CC=C1 XPPWLXNXHSNMKC-UHFFFAOYSA-N 0.000 description 2
- 229920000548 poly(silane) polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- OHUVHDUNQKJDKW-UHFFFAOYSA-N sodium;cyclopenta-1,3-diene Chemical compound [Na+].C=1C=C[CH-]C=1 OHUVHDUNQKJDKW-UHFFFAOYSA-N 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 238000010626 work up procedure Methods 0.000 description 2
- RSSDWSPWORHGIE-UHFFFAOYSA-N $l^{1}-phosphanylbenzene Chemical group [P]C1=CC=CC=C1 RSSDWSPWORHGIE-UHFFFAOYSA-N 0.000 description 1
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 description 1
- ATWLRNODAYAMQS-UHFFFAOYSA-N 1,1-dibromopropane Chemical compound CCC(Br)Br ATWLRNODAYAMQS-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- XFNJYAKDBJUJAJ-UHFFFAOYSA-N 1,2-dibromopropane Chemical compound CC(Br)CBr XFNJYAKDBJUJAJ-UHFFFAOYSA-N 0.000 description 1
- VEFLKXRACNJHOV-UHFFFAOYSA-N 1,3-dibromopropane Chemical compound BrCCCBr VEFLKXRACNJHOV-UHFFFAOYSA-N 0.000 description 1
- YHRUOJUYPBUZOS-UHFFFAOYSA-N 1,3-dichloropropane Chemical compound ClCCCCl YHRUOJUYPBUZOS-UHFFFAOYSA-N 0.000 description 1
- AAAXMNYUNVCMCJ-UHFFFAOYSA-N 1,3-diiodopropane Chemical compound ICCCI AAAXMNYUNVCMCJ-UHFFFAOYSA-N 0.000 description 1
- RBZMSGOBSOCYHR-UHFFFAOYSA-N 1,4-bis(bromomethyl)benzene Chemical compound BrCC1=CC=C(CBr)C=C1 RBZMSGOBSOCYHR-UHFFFAOYSA-N 0.000 description 1
- SWJPEBQEEAHIGZ-UHFFFAOYSA-N 1,4-dibromobenzene Chemical compound BrC1=CC=C(Br)C=C1 SWJPEBQEEAHIGZ-UHFFFAOYSA-N 0.000 description 1
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- AZUCPFMKPGFGTB-UHFFFAOYSA-N 2,2-diiodopropane Chemical compound CC(C)(I)I AZUCPFMKPGFGTB-UHFFFAOYSA-N 0.000 description 1
- IUFVGONBAUNAOT-UHFFFAOYSA-N 2,4,5-trichloro-6-methylpyrimidine Chemical compound CC1=NC(Cl)=NC(Cl)=C1Cl IUFVGONBAUNAOT-UHFFFAOYSA-N 0.000 description 1
- JDSQBDGCMUXRBM-UHFFFAOYSA-N 2-[2-(2-butoxypropoxy)propoxy]propan-1-ol Chemical compound CCCCOC(C)COC(C)COC(C)CO JDSQBDGCMUXRBM-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 1
- YPSXFMHXRZAGTG-UHFFFAOYSA-N 4-methoxy-2-[2-(5-methoxy-2-nitrosophenyl)ethyl]-1-nitrosobenzene Chemical compound COC1=CC=C(N=O)C(CCC=2C(=CC=C(OC)C=2)N=O)=C1 YPSXFMHXRZAGTG-UHFFFAOYSA-N 0.000 description 1
- IZSHZLKNFQAAKX-UHFFFAOYSA-N 5-cyclopenta-2,4-dien-1-ylcyclopenta-1,3-diene Chemical group C1=CC=CC1C1C=CC=C1 IZSHZLKNFQAAKX-UHFFFAOYSA-N 0.000 description 1
- PYISUHMJDDDEAC-UHFFFAOYSA-L C[Nb](C)(C)(Cl)Cl Chemical compound C[Nb](C)(C)(Cl)Cl PYISUHMJDDDEAC-UHFFFAOYSA-L 0.000 description 1
- YBPIUAVRKFOELI-UHFFFAOYSA-N C[Nb](C)C Chemical group C[Nb](C)C YBPIUAVRKFOELI-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 229940045985 antineoplastic platinum compound Drugs 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 150000001495 arsenic compounds Chemical class 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical class B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- YMEKEHSRPZAOGO-UHFFFAOYSA-N boron triiodide Chemical compound IB(I)I YMEKEHSRPZAOGO-UHFFFAOYSA-N 0.000 description 1
- IYYIVELXUANFED-UHFFFAOYSA-N bromo(trimethyl)silane Chemical compound C[Si](C)(C)Br IYYIVELXUANFED-UHFFFAOYSA-N 0.000 description 1
- 125000005997 bromomethyl group Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- SWAKCLHCWHYEOW-UHFFFAOYSA-N chloro selenohypochlorite Chemical compound Cl[Se]Cl SWAKCLHCWHYEOW-UHFFFAOYSA-N 0.000 description 1
- OJZNZOXALZKPEA-UHFFFAOYSA-N chloro-methyl-diphenylsilane Chemical compound C=1C=CC=CC=1[Si](Cl)(C)C1=CC=CC=C1 OJZNZOXALZKPEA-UHFFFAOYSA-N 0.000 description 1
- 125000002603 chloroethyl group Chemical group [H]C([*])([H])C([H])([H])Cl 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 229960000359 chromic chloride Drugs 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000000950 dibromo group Chemical group Br* 0.000 description 1
- VJIYRPVGAZXYBD-UHFFFAOYSA-N dibromosilane Chemical class Br[SiH2]Br VJIYRPVGAZXYBD-UHFFFAOYSA-N 0.000 description 1
- YQECBLVSMFAWIZ-UHFFFAOYSA-N dichloro(dimethyl)germane Chemical compound C[Ge](C)(Cl)Cl YQECBLVSMFAWIZ-UHFFFAOYSA-N 0.000 description 1
- DBPAIFATCNQGFH-UHFFFAOYSA-L dichloro(dimethyl)plumbane Chemical compound C[Pb](C)(Cl)Cl DBPAIFATCNQGFH-UHFFFAOYSA-L 0.000 description 1
- PKKGKUDPKRTKLJ-UHFFFAOYSA-L dichloro(dimethyl)stannane Chemical compound C[Sn](C)(Cl)Cl PKKGKUDPKRTKLJ-UHFFFAOYSA-L 0.000 description 1
- ISXUHJXWYNONDI-UHFFFAOYSA-L dichloro(diphenyl)stannane Chemical compound C=1C=CC=CC=1[Sn](Cl)(Cl)C1=CC=CC=C1 ISXUHJXWYNONDI-UHFFFAOYSA-L 0.000 description 1
- GNEPOXWQWFSSOU-UHFFFAOYSA-N dichloro-methyl-phenylsilane Chemical compound C[Si](Cl)(Cl)C1=CC=CC=C1 GNEPOXWQWFSSOU-UHFFFAOYSA-N 0.000 description 1
- IMDXZWRLUZPMDH-UHFFFAOYSA-N dichlorophenylphosphine Chemical compound ClP(Cl)C1=CC=CC=C1 IMDXZWRLUZPMDH-UHFFFAOYSA-N 0.000 description 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical class Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
- JUUVKOUSGRIGLL-UHFFFAOYSA-N diethyllead Chemical compound CC[Pb]CC JUUVKOUSGRIGLL-UHFFFAOYSA-N 0.000 description 1
- LXKLAFGSADZFAV-UHFFFAOYSA-L diethyllead(2+);dichloride Chemical compound [Cl-].[Cl-].CC[Pb+2]CC LXKLAFGSADZFAV-UHFFFAOYSA-L 0.000 description 1
- KJKXXYRKKOXXDG-UHFFFAOYSA-N diiodo(phenyl)borane Chemical compound IB(I)C1=CC=CC=C1 KJKXXYRKKOXXDG-UHFFFAOYSA-N 0.000 description 1
- ZYMCGHKVJXMQRR-UHFFFAOYSA-N dimethylarsenic Chemical compound C[As]C ZYMCGHKVJXMQRR-UHFFFAOYSA-N 0.000 description 1
- RUIGDFHKELAHJL-UHFFFAOYSA-N dimethylgermane Chemical compound C[GeH2]C RUIGDFHKELAHJL-UHFFFAOYSA-N 0.000 description 1
- XKSLEJLZTDEXGB-UHFFFAOYSA-N dimethyllead Chemical compound C[Pb]C XKSLEJLZTDEXGB-UHFFFAOYSA-N 0.000 description 1
- PWEVMPIIOJUPRI-UHFFFAOYSA-N dimethyltin Chemical compound C[Sn]C PWEVMPIIOJUPRI-UHFFFAOYSA-N 0.000 description 1
- YFEPPSDKRDHTLB-UHFFFAOYSA-N diphenylantimony Chemical compound C=1C=CC=CC=1[Sb]C1=CC=CC=C1 YFEPPSDKRDHTLB-UHFFFAOYSA-N 0.000 description 1
- VITHRHRYZSQDDQ-UHFFFAOYSA-N diphenyllead Chemical group C=1C=CC=CC=1[Pb]C1=CC=CC=C1 VITHRHRYZSQDDQ-UHFFFAOYSA-N 0.000 description 1
- VCYWRKSVJFJVTB-UHFFFAOYSA-L diphenyllead(2+);dichloride Chemical compound C=1C=CC=CC=1[Pb](Cl)(Cl)C1=CC=CC=C1 VCYWRKSVJFJVTB-UHFFFAOYSA-L 0.000 description 1
- KUCPUSUXIGWHFB-UHFFFAOYSA-N diphenyltin Chemical compound C=1C=CC=CC=1[Sn]C1=CC=CC=C1 KUCPUSUXIGWHFB-UHFFFAOYSA-N 0.000 description 1
- KCIDZIIHRGYJAE-YGFYJFDDSA-L dipotassium;[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] phosphate Chemical compound [K+].[K+].OC[C@H]1O[C@H](OP([O-])([O-])=O)[C@H](O)[C@@H](O)[C@H]1O KCIDZIIHRGYJAE-YGFYJFDDSA-L 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- BBIDBFWZMCTRNP-UHFFFAOYSA-N ethylalumane Chemical group CC[AlH2] BBIDBFWZMCTRNP-UHFFFAOYSA-N 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- VABNKPWLESVOJG-UHFFFAOYSA-N ethylboron Chemical compound [B]CC VABNKPWLESVOJG-UHFFFAOYSA-N 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229940093920 gynecological arsenic compound Drugs 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 150000005826 halohydrocarbons Chemical group 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- DBKDYYFPDRPMPE-UHFFFAOYSA-N lithium;cyclopenta-1,3-diene Chemical compound [Li+].C=1C=C[CH-]C=1 DBKDYYFPDRPMPE-UHFFFAOYSA-N 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- BRQVULKQFDNFJE-UHFFFAOYSA-N methyl(phenyl)tin Chemical compound C[Sn]C1=CC=CC=C1 BRQVULKQFDNFJE-UHFFFAOYSA-N 0.000 description 1
- GMOGOLYMNFKVIC-UHFFFAOYSA-L methyl(phenyl)tin(2+);dichloride Chemical compound C[Sn](Cl)(Cl)C1=CC=CC=C1 GMOGOLYMNFKVIC-UHFFFAOYSA-L 0.000 description 1
- NRQNMMBQPIGPTB-UHFFFAOYSA-N methylaluminum Chemical compound [CH3].[Al] NRQNMMBQPIGPTB-UHFFFAOYSA-N 0.000 description 1
- YSTQWZZQKCCBAY-UHFFFAOYSA-L methylaluminum(2+);dichloride Chemical compound C[Al](Cl)Cl YSTQWZZQKCCBAY-UHFFFAOYSA-L 0.000 description 1
- QLWFRFCRJULPCK-UHFFFAOYSA-N methylantimony Chemical compound [Sb]C QLWFRFCRJULPCK-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- FOTXTBSEOHNRCB-UHFFFAOYSA-N methylgermane Chemical group [GeH3]C FOTXTBSEOHNRCB-UHFFFAOYSA-N 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 150000002822 niobium compounds Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 150000002835 noble gases Chemical class 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- IEKVHGDUBCZHRB-UHFFFAOYSA-N phenylarsenic Chemical group [As]C1=CC=CC=C1 IEKVHGDUBCZHRB-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- UBOGEXSQACVGEC-UHFFFAOYSA-K phenyltin(3+);trichloride Chemical compound Cl[Sn](Cl)(Cl)C1=CC=CC=C1 UBOGEXSQACVGEC-UHFFFAOYSA-K 0.000 description 1
- 239000005054 phenyltrichlorosilane Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- AIFMYMZGQVTROK-UHFFFAOYSA-N silicon tetrabromide Chemical compound Br[Si](Br)(Br)Br AIFMYMZGQVTROK-UHFFFAOYSA-N 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical group [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- CRHIAMBJMSSNNM-UHFFFAOYSA-N tetraphenylstannane Chemical compound C1=CC=CC=C1[Sn](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 CRHIAMBJMSSNNM-UHFFFAOYSA-N 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- 238000010555 transalkylation reaction Methods 0.000 description 1
- 125000004665 trialkylsilyl group Chemical group 0.000 description 1
- KBSUPJLTDMARAI-UHFFFAOYSA-N tribromo(methyl)silane Chemical compound C[Si](Br)(Br)Br KBSUPJLTDMARAI-UHFFFAOYSA-N 0.000 description 1
- FEFXFMQVSDTSPA-UHFFFAOYSA-N trichloro(methyl)germane Chemical compound C[Ge](Cl)(Cl)Cl FEFXFMQVSDTSPA-UHFFFAOYSA-N 0.000 description 1
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- HTDIUWINAKAPER-UHFFFAOYSA-N trimethylarsine Chemical compound C[As](C)C HTDIUWINAKAPER-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- PORFVJURJXKREL-UHFFFAOYSA-N trimethylstibine Chemical compound C[Sb](C)C PORFVJURJXKREL-UHFFFAOYSA-N 0.000 description 1
- HVYVMSPIJIWUNA-UHFFFAOYSA-N triphenylstibine Chemical compound C1=CC=CC=C1[Sb](C=1C=CC=CC=1)C1=CC=CC=C1 HVYVMSPIJIWUNA-UHFFFAOYSA-N 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical class [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- QMBQEXOLIRBNPN-UHFFFAOYSA-L zirconocene dichloride Chemical compound [Cl-].[Cl-].[Zr+4].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 QMBQEXOLIRBNPN-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
- C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
- C04B35/571—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide obtained from Si-containing polymer precursors or organosilicon monomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/60—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which all the silicon atoms are connected by linkages other than oxygen atoms
Definitions
- the invention relates to a method for producing heterocouple-containing polycarbosilanes.
- polycarbosilanes and polycarbosilane derivatives are used as polymer precursors for the production of ceramic fibers by the so-called polymer precursor method (precursor method).
- the polycarbosilane polymers are first produced.
- Such polycarbosilanes are polymers with a framework structure consisting of the elements carbon and silicon, the polymers being composed of a framework with a main chain of (-Si-CH 2 -) in which two side chain groups are bonded to each Si atom.
- the polycarbosilanes are then spun into polymer fibers, for example, which can be converted into a ceramic SiC fiber by pyrolysis processes in a non-oxidizing atmosphere.
- the polycarbosilanes In order to be able to serve as a precursor for the pyrolytic production of a ceramic fiber, the polycarbosilanes must be able to be converted into the ceramic fiber with high yields and while maintaining the original polymer morphology, ie while maintaining a fiber shape pre-formed from the polymer.
- fiber production is often used instead of the desired SiC formation, depending on the type of used Polycarbosilane, to a greater or lesser extent melting processes, decomposition reactions with the formation of large, volatile molecules, shrinkage processes and weight loss were observed; the properties of the SiC products which form are negatively influenced by such side reactions and therefore often prove to be unusable.
- PBDPSO polyborodiphenylsiloxane
- Mt metal, eg Ti or Zr
- siloxane units -Si -O- have added to the polycarbosilanes as sintering aids in pyrolysis for fiber production.
- heterocouples such as B, Ti, Zr, Cr, Mo and other than metal oxane units -Mt-O- are also incorporated into the framework of polycarbosilanes; these polymetallocarbosilanes of the prior art are thus derived from polycarbosilanes, the main chain structure of which is essentially formed from structural units —Si-CH 2 - and metal oxane units —Mt-O-.
- Polymetallocarbosilanes such as polytitanocarbosilane, polycarbosilanes are also added as binders and sintering aids for pyrolytic processing.
- the heterocouple is always bound to the silicon atoms of the polycarbosilane via oxygen atoms. Accordingly, only ceramic fibers can be produced from these polycarbosilane derivatives containing heterocouples, which inevitably also always contain oxygen. However, in order to improve the properties of the ceramic fibers, it is often desirable to set the proportion of oxygen in the ceramic fiber as low as possible. There is therefore a need for heterocouple-containing polycarbosilanes in which no oxygen is present and the heterocouple is thus built into the polycarbosilane skeleton without oxygen bridges.
- US Pat. No. 4,987,201 contains boron-containing polymeric Si compounds which are produced by reacting vinylsilanes with boranes, but which can only be crosslinked via the heterocouple.
- EP 375 994 describes new polycarbosilanes which can be prepared directly from the corresponding monomers. However, the options for installing heterocouples are not shown.
- the object was therefore to provide a process for the preparation of polycarbosilanes containing heterocouples which avoids the disadvantages of the prior art, i.e. the polycarbosilane produced are oxygen-free and the heterocouple is built into the polycarbosilane skeleton in such a way that silicon atoms are substituted by the heterocouple.
- the polycarbosilanes prepared according to the invention thus contain, in addition to the polycarbosilane structural units of the formula I, also heterocouple structural units of the formula II.
- heterocouple in the sense of the invention here encompasses the elements M listed above, which are incorporated into the heterocouple polycarbosilane instead of silicon atoms can. These heterocouples are therefore connected to the rest of the polycarbosilane units in the skeleton of the heterocouple polycarbosilane just like the silicon atoms via alkylene radicals or arylene radicals A.
- the polycarbosilanes are oxygen-free and thus differ in this respect particularly advantageously from the oxygen-containing polycarbosilane compounds of the prior art, such as, for example, the polymetallocarbosilanes with the metal oxane units -Mt-O-.
- R i can optionally also be present other analogous organic radicals in these groups.
- An example of a special analog organic radical R i is Trimethylsilylmethyl group (CH 3 ) 3 Si-CH 2 -.
- the M groups of the heterocouples such as boron, selenium, tellurium, chromium and manganese should be mentioned in particular.
- Lower alkyl is a C1 to C4 alkyl radical, but especially methyl or ethyl.
- index 1 stands in particular for the value 1.
- Examples of such preferred M (R i ) k groups in the heterocouple structural units of the formula II are in particular the phenylboron group and the dicyclopentadienyltitanium, dicyclopentadienylzirconium and dicyclopentadienylhafnium group.
- the heterocouple-containing polycarbosilanes consist of a number of different structural units of the general formulas I and II which are present side by side. Both the heterocouple structural units of the formula II and the carbosilane structural units of the formula I can differ in the radicals A. In addition, the carbosilane structural units of the formula I can also differ in the substituents R 1 and / or R 2 .
- the structural units of the general formulas I and II which comprise the heterocouple and are generally of the formulas I and II are combinations of no more than a maximum of three differently substituted Si units and of no more than a maximum of three different A units with one heterocouple structural unit.
- A has only one meaning in all structural units of the general formulas I and II of the heterocouple-containing polycarbosilane; then e.g. those polycarbosilanes in which the structural units of the general formulas I and II are composed of combinations of no more than three differently substituted Si units and one M unit with only one A unit.
- the substituents R 1 and R 2 in all the structural units of the general formula I of polycarbosilane in the Si units each have only a single meaning.
- the heterocouple-containing polycarbosilanes only one type of the structural units of the general formulas I and II is present in the heterocouple-containing polycarbosilanes.
- the R 1 R 2 Si units, the (R i ) k M hetero element units and the A units are then identical in all corresponding structural units of the polycarbosilane based on the general formulas I and II.
- the radical R 1 in a variant of the invention in the polycarbosilanes prepared according to the invention can be hydrogen.
- the radicals R 1 and / or R 2 in the Si structural units of the formula I can be alkyl;
- alkyl has the meaning of a saturated or unsaturated straight-chain or branched alkyl radical, which can optionally be further substituted by inert radicals.
- alkyl examples are methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, dodecyl, hexydecyl, isopropyl, isobutyl, tertiary butyl or allyl.
- the radicals R 1 and / or R 2 in the Si structural units of the formula I can also represent cycloalkyl; Cycloalkyl then has the meaning of a saturated or unsaturated cycloalkyl radical which is optionally further substituted by inert radicals.
- cycloalkyl examples are cyclopentyl, cyclohexyl, cyclopentenyl or cyclohexenyl.
- radicals R 1 and / or R 2 in the Si structural units of the formula I can also represent aryl; Aryl then has the meaning of an unsubstituted or inertly substituted aromatic hydrocarbon radical.
- aryl are phenyl, naphthyl, p-diphenyl or alkylaryl radicals such as tolyl, ethylphenyl or Propylphenyl.
- the radicals R 1 and / or R 2 can also be arylalkyl; Examples of arylalkyl groups are phenylmethyl or phenylethyl.
- the substituent R 1 is hydrogen, lower alkyl or phenyl.
- the radical R 2 also represents lower alkyl or phenyl.
- lower alkyl represents the radicals R 1 and / or R 2 with the meaning of a C1 to C4 alkyl radical, in particular methyl, ethyl, propyl or butyl.
- the very preferred R 1 R 2 Si groups are hydrogenmethylsilylene groups, hydrogenethylsilylene groups, hydrogenphenylsilylene groups, dimethylsilylene groups, methylphenylsilylene groups or diphenylsilylene groups.
- the bridge unit A ie the structural element connecting the Si units and heterocouple units, can stand for a straight-chain or branched alkylene radical in the heterocouple polycarbosilanes produced according to the invention.
- a very particularly preferred alkylene radical A is methylene.
- the bridge unit A can also be an arylene radical.
- Arylene residues include, in particular, residues such as phenylene (for example p-phenylene of the formula -C 6 H 4 -) or p-phenylenedimethylene radicals such as for example -CH 2 -C 6 H 4 -CH 2 - understood.
- the molar ratio in which the structural units of the formulas I and II are present in the hetero-element polycarbosilane can vary within a wide range such that the proportion of the hetero-element structural unit of the formula II in the polycarbosilane is of low molar proportions, e.g. from 1 mol% up to 50 mol%.
- Preferred heterocouple polycarbosilanes of the invention are distinguished in that the structural units of the formulas I and II are present in the polycarbosilane in a molar ratio of 99: 1 to 1: 1, in particular in a molar ratio of 19: 1 to 1: 1.
- the number of structural units which form the heterocouple-containing polycarbosilanes is generally from 10000, preferably up to 100.
- the polycarbosilanes containing heteroatoms therefore have average molecular weights in the range up to 500,000 g / mol.
- the polycarbosilanes based on the structural units of the formulas I and II can have different end groups.
- the end groups can, for example, be halosilyl groups and / or halohydrocarbon groups, on the one hand, or chain termination groups, such as trialkylsilyl groups or lower alkyl groups, on the other hand.
- end groups are dimethylchlorosilyl, dimethylbromosilyl, phenylmethylchlorosilyl, phenylmethylbromosilyl, diphenylchlorosilyl, diphenylbromosilyl, haloalkyl groups such as chloromethyl, bromomethyl, chloroethyl, bromethyl, chlorocyclohexyl, or Chain termination groups such as trimethylsilyl, diphenylmethylsilyl, triphenylsilyl or methyl or ethyl.
- the polycarbosilanes produced according to the invention are solid or liquid, waxy, amorphous or else crystalline materials with a structure in which essentially every silicon atom and each hetero element is only bonded to carbon atoms.
- These polycarbosilanes containing heteroatoms are distinguished by the fact that they have a Si-Si bond fraction of at most 20% and, if need be, only to a small extent have hetero-element-hetero-element bonds. In the examples, the Si-Si bond fraction is even below 5%.
- process variant a the starting materials of the formulas V, VI and VII in an organometallic condensation reaction in the presence of an alkali metal to give the hetero-element polycarbosilanes;
- process variant b the starting materials of the formulas V, VI and VII, on the other hand, are converted in a Grignard reaction in the presence of magnesium to give the heteroatom polycarbosilanes.
- halogen atom-containing hetero-element compounds of the formula VII are used, in which R i , M, Z, k and 1 have the above meanings.
- hetero element compounds of the formula VII used in the process according to the invention are known per se and, moreover, are either commercially available or can be easily prepared by processes known per se. Since the availability of the heterocouple compounds of the formula VII used is therefore not a problem for the person skilled in the art, their preparation is to be briefly outlined here using only a few representative examples.
- alkyl-substituted hetero-element compounds can be derived from them by transalkylation reactions with, for example, aluminum trialkyls produce lying hetero-element halides; for example, the ethyl boron dichloride can be formed by reacting aluminum triethyl with boron trichloride and then easily obtained from the reaction mixture by separation by distillation.
- Phenyl-substituted heterocouple compounds can be prepared in a manner analogous to that of the alkyl-substituted heterocouple compounds.
- the phenylboron dichloride can be obtained by reacting tetraphenyltin with boron trichloride, phenyltin trichloride being obtained as a further product; the phenyl boron dichloride can be obtained from the reaction mixture by separation by distillation.
- Cyclopentadienyl-substituted hetero-element compounds can easily be obtained by reacting the underlying metal chlorides (e.g.
- MCl 4 with cyclopentadienyl sodium or cyclopentadienyllithium (NaC 5 H 5 or LiC 5 H 5 ) or with dicyclopentadienyl magnesium (Mg (C 5 H 5 ) 2 ) are produced and can be obtained by distilling off the solvent used for the reaction (usually xylene or THF) by solvent extraction (for example with chloroform) from the remaining solid residue.
- solvent used for the reaction usually xylene or THF
- solvent extraction for example with chloroform
- di- ⁇ -cyclopentadienyl dihalides namely the bromides or iodides
- these hetero elements can be prepared, for example, from the above chlorides by re-halogenation with boron tribromide or boron triiodide.
- the number of cyclopentadienyl radicals in the heteroelement compounds of the formula VII can also be varied by a number of moles controlled by cyclopentadienyl transfer of dicyclopentadienylmagnesium to the chlorides of the hetero elements, for example to titanium tetrachloride;
- ⁇ -cyclopentadienyl-titanium trichloride can be prepared in this way.
- Cyclopentadienyl residues can be varied;
- ⁇ -cyclopentadienyl-titanium trichloride is also obtained by reacting dicyclopentadienyl-titanium dichloride with titanium tetrachloride.
- the di- ⁇ -cyclopentadienyl heterocouple dichlorides can be prepared, as indicated below for niobium, for example.
- dicyclopentadienyl niobium dichloride is produced from niobium pentachloride and cyclopentadienyl sodium in a one-pot process using a p-oxo complex of the composition [ ⁇ NbCl ( ⁇ -C 5 H 5 ) 2 ⁇ 2 O] Cl 2 , which is subsequently converted into tin by reduction with tin dichloride Product is transferred.
- Cyclopentadienyl-substituted hetero-element compounds of the formula VII can be obtained, for example, in the case of palladium by reacting cyclooctadiene with palladium dichloride, which was previously dissolved in concentrated hydrochloric acid and then diluted in ethanol.
- the cyclooctadiene is produced, for example, with dipotassium tetrachloroplatinate (K 2 [PtCl 4 ]).
- dihalosilanes of the formula V which are known per se are used as the second reaction component, in which R 1 , R 2 and X have the meaning given above.
- dihalosilanes which are suitable for carrying out the process according to the invention are dihalosilanes of the general formula V, in particular dichlorosilanes or dibromosilanes, in which R 1 is hydrogen and R 2 then represents alkyl, cycloalkyl, arylalkyl or aryl or such dihalosilanes of the formula IV in which R 1 and / or R 2 represent alkyl, cycloalkyl, arylalkyl or aryl.
- R 1 is hydrogen on the one hand, lower alkyl having 1 to 4 carbon atoms, ie in particular methyl, ethyl, propyl or butyl, or phenyl;
- R 2 is also lower alkyl with the meaning given above or phenyl.
- dihalosilanes which are particularly suitable for carrying out the process according to the invention are hydrogenmethylsilyldichloride, hydrogenethyldichlorosilane, hydrogenphenyldichlorosilane, dimethyldichlorosilane, diethyldichlorosilane, methylphenyldichlorosilane and diphenyldichlorosilanes and the corresponding dhenlorosilanes.
- the third reaction component used in both process variants a) and b) is a dihalohydrocarbon of the formula VI, known per se, in which A and Y have the meaning given above.
- A can thus represent a straight-chain or branched alkylene radical; C1 to C6 alkylene radicals are advantageous, but especially the C1 to C3 alkylene radicals are methylene, ethylene, trimethylene or propylene.
- Particularly suitable dihalohydrocarbons for the process according to the invention are diiodine, dibromo or dichlorohydrocarbons.
- dihalohydrocarbons examples include methylene chloride, methylene bromide, 1,2-dichloroethane, 1,2-dibromoethane, 1,3-dichloropropane, 1,3-dibromopropane, 1,3-diiodopropane and 1,2-dibromopropane.
- the dihalohydrocarbon of the formula VI can also be an aromatic dihalohydrocarbon.
- aromatic dihalohydrocarbons can be, for example, dihalobenzene or dihaloxylene derivatives such as, in particular, p-dibromobenzene (Br-C 6 H 4 -Br) -Br) or p-di- (bromomethyl) benzene (BrCH 2 -C 6 H 4 -CH 2 Br) .
- the hetero element compound of the formula VII with at least one dihalosilane of the general formula V and with at least one dihalohydrocarbon of the general formula VI in the presence of an alkali metal or magnesium.
- the method according to the invention thus provides a simple and generally applicable method for the convenient preparation of the heterocouple-containing polycarbosilanes based on the structural units of the formulas I and II.
- the process according to the invention enables the production of a large number of interesting hetero element-containing polycarbosilanes based on the structural units of the general formulas I and II.
- the heterocouple compound of the formula VII is reacted with one another with mixtures of differently substituted dihalosilanes of the general formula V and with mixtures of dihalohydrocarbons of the general formula VI with different groups A.
- the reaction of a heterocouple compound with dihalosilane mixtures and with dihalohydrocarbon mixtures gives, for example, heterocouple polycarbosilanes in which different structural units of the general formula I are present side by side, which are independent of one another in the substituents R 1 and / or can distinguish R 2 and / or the radicals A; furthermore, the radicals A can then also differ in different structural units of the general formula II of the heteroatom-containing polycarbosilanes.
- the hetero element compound of formula VII is not more than reacted a maximum of 3 different dihalosilanes and with no more than a maximum of 3 different dihalohydrocarbons at the same time. It is particularly expedient to react the heterocouple compound with mixtures of no more than 3 different dihalosilanes and with only one dihalocarbon or, in another expedient variant, to convert the heterocouple compound with only one dihalosilane and a mixture of a maximum of 3 different dihalocarbons.
- the amount of the dihalosilanes used or their mixtures with the amount of the heterocouple compound used can vary within a wide range from only small proportions of the heterocouple compound up to 50 mol% (based on the sum of dihalosilane and heterocouple compound).
- the amounts of dihalosilanes and hetero element compound are preferably selected so that the molar ratio of all dihalosilanes of the formula V to the hetero element compound of the formula VII is 99: 1 to 1: 1, preferably from 19: 1 to 1: 1.
- the amount of the dihalosilanes and the heterocouple compound used on the one hand and the amount of the dihalohydrocarbons used on the other hand will preferably be such that a molar ratio of the sum of dihalosilanes and heterocouple compound on the one hand to the dihalohydrocarbons on the other hand is approximately 1: 1; in general, deviations from this molar ratio of up to 20% are also possible.
- the hetero element compound of the formula VII is reacted only with a single dihalosilane of the formula V and with only a single dihalohydrocarbon of the formula VI.
- this process variant very uniform chain-like and hetero-element-containing polycarbosilanes are obtained, where the radicals R 1 and R 2 in all structural units of the general formula I of this polycarbosilane and the radical A in all structural units of the general formula I and II of the polycarbosilane each have only a single meaning.
- deviations from the above-mentioned molar ratio with respect to the sum of dihalosilane and heterocouple compound on the one hand and dihalohydrocarbon on the other are possible by up to 20%.
- the trihalosilane RSiX 3 can either be added to the reaction mixture at the start of the reaction of the reactants; however, it can also be added dropwise to the reactant mixture or introduced later in the course of the reaction.
- Examples of trihalosilanes RSiX 3 which can be used are trichlorosilane, methyltribromosilane, methyltrichlorosilane or phenyltrichlorosilane.
- the linear heterocouple-containing polycarbosilane chains can be crosslinked on the basis of general structural formulas I and II by adding tetrahalosilanes such as tetrachlorosilane or tetrabromosilane.
- Crosslinked heterocouple-containing polycarbosilanes based on the structural units of the general formulas I and II are then obtained, which additionally contain branching groups of the formula IV.
- the degree of condensation of the chain-shaped or crosslinked heterocouple-containing polycarbosilanes to be produced can be controlled on the basis of the general structural units of the formulas I and II by stopping the condensation by adding condensation termination reagents.
- Suitable reagents for terminating the condensation reaction are monohalosilanes R '3 SiX, wherein X is halogen, preferably chlorine or bromine, and R' has the meaning given for R 2 above alkyl, cycloalkyl, arylalkyl or aryl; further suitable reagents for stopping the condensation reaction are monohalocarbons R ′′ Y, where Y is iodine, bromine or chlorine and R ′′ is alkyl or cycloalkyl.
- suitable monohalosilanes are trimethylchlorosilane, trimethylbromosilane or diphenylmethylchlorosilane.
- suitable monohalohydrocarbons are methyl bromide or methyl chloride.
- the type of end groups that are present in the hetero element-containing polycarbosilanes produced by the process according to the invention depends on whether the process with or without chain termination reagents.
- the end groups already described above in connection with the polycarbosilanes are obtained.
- heterocouple-containing polycarbosilanes based on structural units of the formulas I and II
- the heterocouple compound of the formula VII, dihalosilanes of the formula V and dihalohydrocarbons of the formula VI are in an inert organic liquid medium with one another in the presence of an alkali metal implemented.
- the alkali metal which can be used in process variant a) according to the invention can be, for example, lithium, sodium or potassium.
- the preferred alkali metal is sodium because it generally gives the highest yields of polycarbosilanes and is the least likely to cause side reactions. To ensure complete implementation, working with a slight excess of alkali metal is preferred.
- the amount of the alkali metal to be used is about 2.2 moles per mole of all the dihalo compounds used, ie about 4.4 moles of alkali metal are required for the reaction of 0.5 mole of hetero element compound, 0.5 mole of dihalosilane and 1 mole of dihalohydrocarbon .
- the organic, liquid medium for process variant a) in which the reaction takes place can be any solvent which is compatible with alkali metals and in which the heterocouple compounds, dihalosilanes and dihalohydrocarbons used as reactants are soluble.
- This organic, liquid medium is preferably also a solvent for the polycarbosilanes to be produced by the process according to the invention.
- Suitable solvents can e.g. Hydrocarbons such as toluene, xylene or paraffins, ethers such as tetrahydrofuran, dioxane or dibutyl ether, alkylene glycol ether, e.g.
- Ethylene glycol ethers such as diethylene glycol dialkyl ether, propylene glycol ether, polyethylene glycol ether or polypropylene glycol ether, but also nitrogen-containing solvents such as ethylene diamine or mixtures thereof.
- Solvents whose boiling temperatures are above the melting point of the alkali metal used are advantageously used.
- a preferred solvent is xylene.
- the amount of solvent is variable over a wide range. The use of large amounts of solvent leads e.g. to low molecular weight polycarbosilanes.
- the alkali metal halides obtained during the reaction are usually insoluble and can therefore be easily removed by filtration.
- Process variant a) can be carried out over a wide range of temperatures, but the reaction temperature is preferably kept at from about 10 to 180 ° C.
- the reaction is exothermic and is preferably started at the melting point of the alkali metal used, for example when using sodium at about 100 ° C. No external heat is required during the reaction. If the reaction is too violent, cooling may also be necessary; in principle, cooling is not mandatory.
- the reaction is generally under an appropriate one Shielding gas carried out. Suitable protective gases are, for example, nitrogen or argon.
- the reaction according to process variant a) is generally carried out in such a way that a suspension of the alkali metal is first generated in the solvent.
- Preferred solvents for producing the suspension are hydrocarbons such as xylene or decalin, into which the alkali metal is introduced in the form of small pieces and then heated to temperatures above the melting point of the alkali metal with vigorous stirring.
- the alkali metal suspension thus obtained can be used either after cooling or directly for the further reaction.
- the remaining reactants heterocouple compound, dihalosilanes, dihalohydrocarbons
- the reactants are mixed with one another before being introduced and, if appropriate, diluted with a suitable solvent.
- the polycarbosilane can be obtained from the reaction mixture of process variant a) by any suitable method. If the polycarbosilane is soluble in the solvent, the other insoluble components can be separated off by filtration. The polycarbosilane remaining in the solvent can be cleaned by washing with water and dried to a powder by removing the solvent. If excess alkali metal has been used, this is solvolysed with a suitable alcohol in a conventional manner before the polycarbosilane is isolated. Suitable alcohols, depending on the alkali metal used, are methanol, Ethanol, isopropanol, tertiary butanol.
- the alkali metal alcoholates formed are then further decomposed by adding water and the precipitated alkali metal salts are removed by filtration.
- the polycarbosilanes formed are insoluble in the solvent, they can be extracted with a suitable other solvent, then cleaned by washing with water and dried to a powder by removing the solvent.
- the magnesium used in process variant b) according to the invention is used as metal in the form of magnesium powder, magnesium chips or magnesium grits etc.
- the magnesium metal can preferably be pretreated for use in the Grignard reaction before use by measures known per se to the person skilled in the art. For example, it is advisable to degrease the magnesium before the reaction and to remove adhering moisture by drying or, if necessary, to etch it with small amounts of lower bromine- or iodine-containing hydrocarbons such as dibromomethane, dibromopropane, diiodopropane etc., but preferably with elemental iodine.
- the amount of the magnesium metal to be used is about 2 mol, based on the sum of the heterocouple compound and dihalosilane used on the one hand and the dibromo hydrocarbon used on the other hand.
- the sum of the quantities of heterocouple compound and dihalosilane is preferably used in an approximately equimolar amount to the dihalohydrocarbon in the reaction according to process variant b).
- the organic solvent in which the Grignard polycondensation reaction (process variant b) takes place can be any dry solvent compatible with Grignard reagents, in particular an ether such as diethyl ether, dioxane, tetrahydrofuran etc.
- the Grignard polycondensation reaction according to the invention (process variant b) is generally carried out, for example, in such a way that initially hetero element compound and dihalosilane with the magnesium in the solvent, preferably in ether or tetrahydrofuran, are initially introduced.
- the dihalohydrocarbon (preferably the bromine derivative) is then added dropwise until the reaction starts and the exothermic reaction is controlled by adjusting the dropping rate of dihalohydrocarbon so that uniform boiling takes place.
- dry reaction conditions should be maintained and the reaction carried out under a protective gas atmosphere and with stirring.
- Suitable protective gases are, for example, nitrogen or noble gases such as argon.
- the temperature which arises during the reaction depends on the boiling point of the solvent used.
- the reaction mixture is generally stirred at room temperature for a long period of time. Typically, the reaction is carried out over a period of 1 to 48 hours.
- Grignard reaction batches For example, residues of unreacted Grignard reagents are added or poured in decomposed in water, hydrochloric acid, aqueous ammonium chloride solution etc.
- the polycarbosilane dissolved in the solvent is separated from the aqueous phase or, if appropriate, extracted from the reaction mixture with a suitable organic solvent, for example with halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride or chlorofluorocarbons, and in itself obtained in a known manner by removing the solvent as a substance.
- a suitable organic solvent for example with halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride or chlorofluorocarbons
- the above process variants according to the invention make it possible in an advantageous manner to produce heterocouple-containing polycarbosilanes directly from monomeric heterocouple compounds, dihalosilanes and dihalohydrocarbons.
- oxygen-containing heterocouple compounds for example polyborodiphenylsiloxane, titanium tetraalkoxides, aluminum trialkoxides, zirconium tetraacetylacetonate, etc.
- the process according to the invention for the production of hetero-element-containing polycarbosilanes a very gentle process that allows these polycarbosilanes to be produced with high purity.
- the method according to the invention also enables the production of oxygen-free heterocouple-containing polycarbosilanes.
- the freedom from oxygen of the heterocouple-containing polycarbosilanes is of particular advantage, particularly with regard to the subsequent thermal conversion into ceramic products.
- the thermal conversion of oxygen-containing polycarbosilane precursors to ceramic products usually takes place with the formation of silicon dioxide and metal oxides and with high weight losses and leads to poorer material properties of the ceramic products obtained.
- the heterocouple-containing polycarbosilanes are suitable as valuable starting polymers (precursors) for the production of technically high-quality silicon carbide ceramic products (e.g. fibers, etc.) as well as for various other technical applications, e.g. as sintering additives, surface impregnation agents, binders or coating materials.
- the yield of solid, yellow polycarbosilane was 30.5 g (98%). Elemental analysis showed 13.4% Si; 80% C; 6.21% H and 0.35% B. The typical polyphenylcarbosilane bands were identified in the IR spectrum. The characteristic BC vibration was detected at 1350 cm -1 .
- the 1 H-NMR spectrum showed peaks at 7.9 ppm (phenyl-B); 7.3 ppm (phenyl-Si) and 0-2.3 ppm (CH 2 ).
- the 11 B NMR spectrum showed a broad signal around 30 ppm.
- the experiment was carried out analogously to Example 1.
- the batch amounts were 0.076 mol of Ph 2 SiCl 2 (19.24 g; 15.98 ml); 0.151 mol CH 2 Br 2 (26.25 g; 10.54 ml) and 0.076 mol PhBCl 2 (12.07 g; 10.04 ml).
- the boron-containing polycarbosilane isolated with 88% yield (19.9 g) was a black-brown, highly viscous product. Elemental analysis showed: 10% Si; 75.9% C; 6.2% H and 2.5% B.
- the IR spectrum showed the expected increase in intensity of the BC vibration band at 1350 cm -1 .
- the data of the 1 H NMR spectrum were: 7.6-8.3 ppm (phenyl-B); 6.3 - 7.7 ppm (phenyl-Si) and 0 - 3 ppm (CH 2 ).
- the B peak was found at about 30 ppm in the 11 B-NMR spectrum.
- the yield of red, hard solid was 85.3% (20.8 g). Elemental analysis showed: 16.1% Si; 75.8% C; 5.1% H; 2.4% Ti.
- the IR spectrum showed the vibrational bands characteristic of polyphenylcarbosilane structures. In addition, the typical absorption bands of the cyclopentadienyl groups were at 1440, 880 and 820 cm -1 . The Ti-C vibration was 520 cm -1 .
- the 13 C-NMR spectrum showed three signal ranges: at 0 to 50 ppm (alkyl), at 114 to 117 ppm (cyclopentadienyl) and at 128 to 136 ppm (phenyl).
- reaction solution was then stirred for a further 16 hours at room temperature, saturated ammonium chloride was added, the organic phase was separated off, filtered and the solvent was distilled on a rotary evaporator.
- the isolated deep red product was dried at 100 ° C. under high vacuum for several hours.
- the yield was 17.55 g (91%) polycarbosilane. Elemental analysis showed: 11.7% Si; 70.4% C; 6% H; 8.4% Ti. The IR spectrum clearly showed cyclopentadienyl and Ti-C characteristic vibration bands. The 1 H-NMR and 13 C-NMR spectra largely corresponded to the spectra of the hetero element polycarbosilane of Example 4.
- the yield of solid, red-brown polycarbosilane was 17.4 g (84%). Elemental analysis showed 15% Si; 65.6% C; 5.4% H; 9.4% Zr. The IR spectrum clearly showed cyclopentadienyl and Zr-C characteristic vibrations. The 1 H and 13 C NMR spectra also characterized a Zr-containing polycarbosilane.
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Claims (11)
- Procédé de préparation non catalytique et non pyrolytique de polycarbosilanes contenant un hétéroélément à base de motifs de formules générales I et IIR1 désigne l'hydrogène ou un groupe alkyle, cycloalkyle, cycloalcényle, arylalkyle ou aryle éventuellement substitué par des restes inertes et/ou ramifié, où R1 peut avoir la même signification ou une signification différente dans les divers motifs d'un seul et même polycarbosilane,R2 désigne un groupe alkyle, cycloalkyle, cycloalcényle, arylalkyle ou aryle éventuellement substitué par des restes inertes et/ou ramifié, où R2 peut avoir la même signification ou une signification différente dans les divers motifs d'un seul et même polycarbosilane,A désigne un groupe alkylène ou arylène à chaîne droite ou ramifiée, où A peut avoir la même signification ou une signification différente dans les divers motifs d'un seul et même polycarbosilane,M désigne un hétéroélément ayant une valence de m = 2, 3, 4 ou 5 choisi parmi B, Al, Ga, Ge, Sn, Pb, P, As, Sb, Se, Te, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Ni, Pd et Pt,(Ri)k désigne un nombre k valant 0, 1, 2 ou 3 de restes Ri identiques ou différents choisis dans le groupe constitué par un alkyle, le phényle, le cyclopentadiényle et le cyclooctadiényle etl prend la valeur 1, 2, 3 ou 4 dans le motif de formule II pour l'indice du groupe A fixé à l'hétéroélément M ayant la signification précédente, dans la mesure où m = k + l + 1, caractérisé en ce qu'il comporte une étape qui consiste à co-condenser au moins un dihalogénosilane de formule générale Vdans laquelleR1, R2 ont les mêmes significations que ci-dessus etX désigne un halogène tel que le chlore ou le brome,avec au moins un hydrocarbure dihalogéné de formule générale VI
Y-A-Y (VI)
dans laquelleA a la même signification que ci-dessus etY désigne un halogène tel que le chlore, le brome ou l'iode,ainsi qu'un composé à base d'hétéroatome halogéné de formule générale VIIM, (Ri)k et l ont les mêmes significations que ci-dessus etZ désigne un halogène tel que le chlore, le brome ou l'iode,en présence d'un métal alcalin ou de magnésium, et si besoin en ajoutant des réactifs de réticulation et/ou d'interruption de chaîne. - Procédé de préparation de polycarbosilanes contenant un hétéroélément selon la revendication 1, caractérisé en ce qu'on utilise un composé à base d'hétéroatome halogéné de formule générale VII, dans laquelle (Ri)k désigne un nombre k valant 1, 2 ou 3 de restes Ri identiques choisis dans le groupe constitué par un alkyle en C1-C4, le phényle, le cyclopentadiényle.
- Procédé selon la revendication 1 ou 2, caractérisé en ce qu'on utilise un composé à base d'hétéroélément de type B ayant une valence de m = 3 et de type Ti, Zr, Hf ayant chacun la valence de m = 4.
- Procédé selon l'une des revendications 1 à 3, caractérisé en ce qu'on utilise un composé de formule générale VII, dans laquelle le groupe R1 désigne phényle dans le cas où l'hétéroélément M a une valence de m = 3 et désigne le cyclopentadiényle dans le cas où l'hétéroélément M a une valence de m = 4.
- Procédé selon l'une des revendications 1 à 4, caractérisé en ce qu'on utilise un composé à base d'hétéroélément de formule générale VII, dans laquelle l a pour valeur 1.
- Procédé selon l'une des revendications 1 à 5, caractérisé en ce qu'on utilise un hydrocarbure dihalogéné de formule générale VI, dans laquelle A désigne un groupe alkylène en C1-C6.
- Procédé selon l'une des revendications 1 à 6, caractérisé en ce qu'on utilise un hydrocarbure dihalogéné de formule générale VI, dans laquelle A désigne le méthylène, l'éthylène, le triméthylène ou le propylène.
- Procédé selon l'une des revendications 1 à 7, caractérisé en ce qu'on utilise un un hydrocarbure dihalogéné de formule générale VI, dans laquelle Y désigne le chlore ou le brome.
- Procédé selon l'une des revendications 1 à 8, caractérisé en ce qu'on utilise un dihalogénosilane de formule générale V, dans laquelle R1 et / ou R2 désigne un alkyle en C1-C4, le cyclopentyle, le cyclohexyle, le cyclopentényle ou le cyclohexenyle, le phénylméthyle, le phényléthyle, le phényle, le naphtyle, le p-diphényle, le tolyle, l'éthylphényle ou le propylphényle.
- Procédé selon l'une des revendications 1 à 9, caractérisé en ce qu'on utilise un dihalogénosilane de formule générale V, dans laquelle R1 désigne l'hydrogène, un alkyle en C1-C4 ou le phényle.
- Procédé selon l'une des revendications 1 à 10, caractérisé en ce qu'on utilise un dihalogénosilane de formule générale V, dans laquelle R2 désigne un alkyle en C1-C4 ou le phényle.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4102315 | 1991-01-26 | ||
DE4102315A DE4102315A1 (de) | 1991-01-26 | 1991-01-26 | Heteroelement enthaltende polycarbosilane |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0497171A2 EP0497171A2 (fr) | 1992-08-05 |
EP0497171A3 EP0497171A3 (en) | 1992-09-09 |
EP0497171B1 true EP0497171B1 (fr) | 1997-04-02 |
Family
ID=6423773
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP92100811A Expired - Lifetime EP0497171B1 (fr) | 1991-01-26 | 1992-01-20 | Polycarbosilanes contenant hétéroatomes |
Country Status (5)
Country | Link |
---|---|
US (1) | US5204431A (fr) |
EP (1) | EP0497171B1 (fr) |
JP (1) | JPH05214108A (fr) |
AT (1) | ATE151091T1 (fr) |
DE (2) | DE4102315A1 (fr) |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4127354A1 (de) * | 1991-08-19 | 1993-02-25 | Solvay Deutschland | Granulat auf basis von siliciumcarbidpulver und siliciumcarbidkeramik |
DE4229743A1 (de) * | 1992-09-05 | 1994-03-10 | Solvay Deutschland | Quellfähige, vernetzte, unschmelzbare Polycarbosilane |
DE19741460A1 (de) * | 1997-09-19 | 1999-03-25 | Max Planck Gesellschaft | Synthese borhaltiger Polysilazane durch Hydrosilylierungsreaktionen von Hydridosilylethylboranen mit vinylierten Polysilazanen sowie deren Überführung in keramische Materialien |
DE19741459A1 (de) * | 1997-09-19 | 1999-03-25 | Max Planck Gesellschaft | Synthese borhaltiger Polysilazane durch katalytisch induzierte dehydrierende Kupplungsreaktionen von Hydridosilylethylboranen mit Ammoniak, primären Aminen und polymeren Silazanen sowie deren Überführung in keramische Materialien |
JP4343475B2 (ja) * | 1999-08-24 | 2009-10-14 | 株式会社カネカ | 難燃剤及びこれを用いた難燃性樹脂組成物 |
US20060004169A1 (en) * | 2003-01-10 | 2006-01-05 | Sherwood Walter J Jr | Ceramic-forming polymer material |
GB0309010D0 (en) * | 2003-04-22 | 2003-05-28 | Univ Manchester | Polymer networks |
US7604678B2 (en) * | 2004-08-12 | 2009-10-20 | Hoeganaes Corporation | Powder metallurgical compositions containing organometallic lubricants |
US20170088674A1 (en) * | 2014-08-14 | 2017-03-30 | Institute Of Process Engineering, Chinese Academy Of Sciences | Polymetallocarbosilane from organic metal catalyzed polymerization and uses thereof |
CN104211967B (zh) * | 2014-08-14 | 2017-05-03 | 中国科学院过程工程研究所 | 聚金属碳硅烷及其制备方法和应用 |
JP2020041015A (ja) * | 2018-09-06 | 2020-03-19 | 日本放送協会 | ホウ素含有重合体 |
US11365290B2 (en) | 2019-11-22 | 2022-06-21 | Raytheon Technologies Corporation | Modified preceramic polymers, method of making and ceramic matrix composite formed therefrom |
CA3196581A1 (fr) | 2020-10-30 | 2022-05-05 | Howard Q. SHEN | Composition et preparation pour precurseur ceramique a base de carbure d'hafnium |
CN115894940B (zh) * | 2021-09-30 | 2023-09-15 | 中国人民解放军国防科技大学 | 一种含Zr-C-Si主链单源超高温陶瓷先驱体的制备方法 |
CN114409906A (zh) * | 2021-12-27 | 2022-04-29 | 宁波众兴新材料科技有限公司 | 一种利用液态聚碳硅烷制备聚金属碳硅烷的方法与应用 |
CN116333322B (zh) * | 2023-02-06 | 2024-09-17 | 长沙达菲新材料科技有限公司 | 一种掺硼铝聚碳硅烷及其制备方法和应用 |
CN116639983B (zh) * | 2023-06-05 | 2024-03-22 | 湖南泽睿新材料有限公司 | 一种耐高温的近化学计量比连续碳化硅纤维及其制备方法 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4556526A (en) * | 1980-03-25 | 1985-12-03 | Ube Industries, Ltd. | Process for production of sintered ceramic body |
EP0217129B1 (fr) * | 1985-08-27 | 1989-11-23 | Ube Industries Limited | Peinture résistant à la chaleur et contenant un polymétallocarbosilane |
US4762895A (en) * | 1987-08-10 | 1988-08-09 | Dow Corning Corporation | Process for the preparation of preceramic metallopolysilanes and the polymers therefrom |
US4761458A (en) * | 1987-08-17 | 1988-08-02 | Dow Corning Corporation | Preceramic polycarbosilane derivatives |
EP0315177B1 (fr) * | 1987-11-05 | 1993-08-11 | Ube Industries, Ltd. | Fritte de haute résistance et de grande dureté et son procédé de fabrication |
JPH01252637A (ja) * | 1987-12-11 | 1989-10-09 | Nippon Telegr & Teleph Corp <Ntt> | 有機金属高分子化合物の製造方法 |
DE3841348A1 (de) * | 1988-12-08 | 1990-06-13 | Kali Chemie Ag | Verfahren zur herstellung von polycarbosilanen und neue polycarbosilane |
US4987201A (en) * | 1989-06-05 | 1991-01-22 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Boron-carbon-silicon polymers and the ceramic thereof |
-
1991
- 1991-01-26 DE DE4102315A patent/DE4102315A1/de not_active Withdrawn
-
1992
- 1992-01-20 AT AT92100811T patent/ATE151091T1/de not_active IP Right Cessation
- 1992-01-20 DE DE59208281T patent/DE59208281D1/de not_active Expired - Fee Related
- 1992-01-20 EP EP92100811A patent/EP0497171B1/fr not_active Expired - Lifetime
- 1992-01-21 US US07/822,730 patent/US5204431A/en not_active Expired - Fee Related
- 1992-01-24 JP JP4010891A patent/JPH05214108A/ja active Pending
Also Published As
Publication number | Publication date |
---|---|
DE4102315A1 (de) | 1992-07-30 |
EP0497171A3 (en) | 1992-09-09 |
DE59208281D1 (de) | 1997-05-07 |
JPH05214108A (ja) | 1993-08-24 |
ATE151091T1 (de) | 1997-04-15 |
US5204431A (en) | 1993-04-20 |
EP0497171A2 (fr) | 1992-08-05 |
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